Phosphorus sulfide-turpentine reaction products and lubricants containing the same



Patented Aug. 19, 1952 PHOSPH ORUS SULFIDE-TURPENTINE REAC- TION PRODUCTS AND LUBRICANTS CON- TAINING THE SAME Franklin M. Watkins, Flossmoor, Ill. assignor to Sinclair Refining ,Company, corporation of Maine New York, N. Y., a

' NoDrawing. Application July 19, 1946, 7 Serial N0. 684,777

In the applications of Robert L. May, Serial Numbers 494,687 and 494,698, filed July 14, 1943, now Patent Numbers 2,486,188 and 2,498,133,'respectively, there are described phosphorus sulfide-terpene' condensation products effective in repressing or inhibiting the deterioration of lubricatingoils and the corrosion of metal parts in contact therewith. My invention is concerned with improvements in these products as, prepared from commercial Wood turpentine and fractionated turpentines, including the material sold under the name Pinene 111, which is reported as containing about 92% alpha pin'ene, 4-5% camphene, and 3-4% dipentene and other'terpenes. My invention embraces the-improved products per se as well as-jmineral oil compositions in which they are comprised as addends. It also embraces derivatives of the improved products and oil compositions comprising the derivatives. I I have discovered that the thermal stability of the turpentine-phosphorus sulfide condensates in mineral oils is markedly improved by employing in the reaction yielding the condensate, turpentine which has been pretreated fonthe removal of oxygen compounds. Ihave further discovered that such pretreatment of the turpentine or turpentine fraction greatly improves the odor of compounded oils comprising the condensation product. Heretofore, such oils have been distinguished by an extremelyunpleasant mercaptan-like odor.

It has been known that the commercially available turpentines contain oxygen compounds but it apparently has never before been appreciated that these compounds upon employment of the turpentine in a reaction of the type involved in the May application could afiect the thermal stability of the condensate in mineral oils or impart an undesirable odor thereto. The objectionable odor appears to derive from a reaction between the oxygen compounds and the phosphorus sultide yielding sulfur derivatives of the former.

Although the removal of the oxygen impurities from the turpentine may be accomplished by any suitable method, I prefer to remove them filed June 6, 1946, now Patent No. 2,453,712. Alternatively, the methoddescribed in my copending application Serial No. 674,923, filed June 6,

1946, now Patent No. 2,515,281, or the method'described by George H. Splittgerber in his copending application, Serial No. 674,931, filed June 6, 1946, now Patent No. 2,461,007, may be used, for

example. As will be demonstrated hereinafter, 1

L12 Claims. (01. 252 46.6)

ordinary distillation will not suffice to remove the oxygen impurities nor will treatment with caustic soda, even at elevated temperature, but caustic treatment is sometimes useful as a preliminary measure to reduce peroxide content. In accordance with the method of the Kleinholz pplication, the turpentine is refluxed with an alkali metal alcoholate, 1 hours refluxing being usually sufiicient. The Splittgerber method comprises refluxing of the turpentine over barium oxide,

while the method of my copending application involves metallic sodium as the principal reagent. The reaction between the pretreated turpentine and the phosphorus sulfidaPgSa 01-12283, yielding the condensate is best effected 'at an elevated temperature of the order of 20030091. Since the reaction is quite rapid and highly exothermicatsuch temperatures, it is advisable to the end that it will not become violent and uncontrollable, where substantial portions of the reactantsare involved, to effect mixing of the reactants slowly at a temperature Within the stated range rather than-to pre-mix thereact'ants before applying heat. Despite the fact that the reaction is exothermi heat is usually required to carry it to completion. 1

. Exemplary of the procedure usually followed in the preparation of the condensate: .The turpentine-is placed infa flask and stirred. while being heated to about225 F. The phosphorus sulfide,

in powdered form, is then added slowly with continued stirring in portions of, say, about5% to 10% of the total amount tobe added, and at such a rate that thejtemperature of the reactiondoes not exceed about 250? F. or drop below about 220 F. During. this stage of the reaction no external heat need be applied. Following the additionjof the lastv increment of phosphorus sulfide, heat is supplied to the reaction mixture as necessary to maintain it at'atemperature of 225 FL- 0? F.,

for example. Continuous stirring of the mixture through'o'utfthe reaction is desirable. The reaction is usuallyieomplete in from 2 'to 4 hours.

Upon-itscompletion any excess turpentine may be removed by distillation.

, Although the temperature atwhichthe reaction is conducted is also a factor,- the characteristics of the 'product depend Ichiefiy upon "the proportions of the reactants used. 7 I generally employ from 1130.9 parts by weight of turpentine for each part of sulfide. Within this range' th'eproducts are solid andresin-like upon topping oif excess turpentine-when present.

The condensation products resulting fronil the usefofabout o'r-less of the sulfide'dis'solve compositions.

completely in lubricating oils. Those prepared using 33% to 40% or more of the sulfide contain matter not completely oil-soluble and, accordingly, are less desirable for use in lubricating oil The products as produced using to of phosphorus pentasulfide, P'2S5, are especially advantageous for compounding with mineral oils. P285 with turpentine appears to be about 25% to 28% of the total weight of the reactants.

The lubricating oil composition of my invention may consist solely of the lubricating oil constituent and the turpentine-phosphorus sulfide condensate prepared with deoxygenated turpentine. However, my inhibitor has been found to be compatible with other lubricating oil addends and the inclusion of other addends is with;- in the contemplation of my present invention and constitutes an important aspect thereof. The addition to internal combustion engine lubricants of detergent materials has been found highly desirable. An especially effective lubrieating oil composition, for the lubrication of internal combustion engines and the like, contemplated by the present invention, is one comprising, in addition to the lubricating oil fraction and my inhibitor, a minor proportion of the calcium salt of iso-octyl salicylate or the calcium salt of capryl salicylate. These calcium salts have been found particularly effective as detergents in lubricating oil compositions used in internal combustion engines, as more fully described in the copending applications of Willard L. Finley, Serial No. 407,002, filed August 15, 1941, now Patent No. 2,347,547, and Serial No. 417,471, filed November 1, 1941, now Patent No. 2,339,692.

When used together, the calcium salt and my inhibitor have been found to complement each other so that the effectiveness of each is promoted. The phosphorus acidity of the inhibitor appears to be neutralized by the calcium salt,

any tendency of the former to promote sludge formation being thereby minimized, while the compositions may be varied somewhat but in any case only a minor proportion is used. In the absence of other addends, generally' satisfactory results have been obtained by using proportions within the range of about 0.01% to about 0.5%, based on the weight of the lubricatingoil constituent. In special cases, for example, when calcium salt detergents are present, somewhat higher proportions, say up to about 1%, may be used with advantage. In gear lubricants. these turpentine-Pass condensation products have been found to increase the film strength of the lubricant and, for such purposes, proportions somewhat in excess of those previously noted may be used. However, these condensation products are acidic phosphorus derivatives and phosphorus acidity has been found to have a general tendency to cause polymerization and sludge formation in mineral lubricating oil. In internal combustion engine lubricants, where sludge formations must be minimized, the use of the condensation product in proportions exceeding 0.5% by weight, in the absence of detergents such as previously noted, is not generally advisable. However, proportions within the indicated range of about 0.01% to 0.5% have not been found to causenoticeable or objectionable sludging under The combining equivalent of such conditions. Proportions within the range of about 0.05% to 0.10% are particularly recommended in the preparation of my lubricating oil composition for use in internal combustion engines in the absence ofa detergent.

residual phosphorus acidity may remain with its characteristic tendency toward sludge formation.

- The optimum ratio of the inhibitor to the detergent will depend upon the basicity of the detergent and upon the amount of P285 equivalent in the inhibitor, and may be determined for any particular set of conditions by simple tests.

Detergents other than the above calcium salts which may be used, with advantage, in my mineral oil compositions include the barium phenolate of sulphurized diamyl phenol, currently marketed under the trade name Aerolube. BF; metallic phenolates of sulphurized tertiary amyl phenol, such as currently.marketedunder-the trade names Calcium Paranox and Barium Paranox; a basic calciumidetergent currently marketed under the trade name C. M..2A; and

various metallic soaps, metallic sulfonates, alcoholates or alkoxides and wax-alkylated salicylic acid salts.

As the mineral oil constituents of my improved lubricating oil composition, various petroleum lubricating oil fractions may be used, for instance solvent-treated Mid-Continent neutral or a blend of such Mid-Continent neutral and bright stock or a solvent-refined lubricating oil fraction from a Pennsylvania crude. Characteristics of several such oils which have been used with advantage are given in the following Table I in which-Oil A,

is a solvent-treated Mid-Continent neutral blended with 42% bright stock, Oils B andE are "TABLE I] BASEOIL A B o I n V .E

27.1 I 28.4 29.5, g ade 470 540 405,-v 400 525 610' 480 t 545 finals 1,526.7. 249.0 550.7

57.7 121.7 49 62.6 80.0 106 92.7 79. 2 5 10 5- a 0 .04 .58 .039 5.06 None None None .004 AcidNo r .02 .025 .075 (Sjauonification No. .16

oorm; 6- 3y- 5- 3 suuuapercemun nflu W26 .1 31 .11 a 20 My condensation productsprior to orfollowing their additionjtov lubricating oils may bere- "acted with other substances with the production zinc oxide, for example; .The condensates of my invention may, in other words, be dealtwith in the same way as the products of May "application, Serial No. 494,687 previously mentioned herein.

'fiux at 350 F. for 16 hours.

in this connection, reference ismade to May Patents 2,356,073, granted August 15, 1944; 2,356,074, granted August 15, 1944; 2,392,252, granted January 1, 1946; 2,392,253, granted January 1, 1946; 2,379,312, granted June 26, 1946; and 2,379,313, granted June 26, 1945; and to May applications-Serial Nos. 545,193, now Patent No. 2,409,877, and 545,195, now Patent No. 2,409,878, both filed July 15, 1944.

Various aspects of my invention are illustrated by the following examples which are not to'be taken as in any way restrictive of the scope thereof. The examples will be noted as in part comparative. I 9

Example 1- A 1400 gram sample of Pinene 111 is refluxed for approximately 1 hours with 28 grams of sodium methylate powder following which the mix! ture is subjected to a distillation'in'which a fraction boiling at 156157 C. is taken as the product.

Phosphorus pentasulfide is reacted with the thus purified turpentine fraction to obtain an oil soluble product conforming substantially to the characteristics indicated in the table below. The

A portion of the topped product is blended with 102 grams of a lowviscosity Mid-Continent oil. 2% parts by weight of the resulting oil concentrate, after filtration to remove any insolubles,

is mixed with 97% parts by Weight-of a Mid- Continent 20 or 30 motor oil. The odor of such a blend is much less offensive than that of a blend comprising a turpentine-phosphorus sulfide reaction product prepared with turpentine or Pinene 111 which has not been subjected to the alcoholate or similar treatment.

A second preparation with P285 (88 gms.) dissolved in 400 gms. turpentine is heated under re- No decomposition as would be indicated by the formation of a precipitate occurs. A precipitate is formed in 2 hours and progressively increases in quantity on 'further heating in the case of the turpentinesulfide product as prepared with turpentine which has not been subjected to pretreatment for the removal of oxygen compounds.

Example 2 table also gives suitable reaction conditions.

TABLE II Turpentine:

Grams 368 Mols 2.7 Phosphorus pentasulfide:

Grams 111 Mols 0.5 M01 ratio (turpentine/Pass) .4/1 Reaction time (hours) 1 I 4 Reaction temperature (F. 275 Atmosphere 'Air Stirring Yes Reaction product: I j j Weight after filtering and topping 359 Weight per cent of P2S5 reacted' 100 Phosphorus, per cent 8.10 Sulfur, per cent 21.7 Acid No. 42.2 Saponification No. 138,1 Mols turpentine reacted per mol of P285 Q. 3.84/1 Solubility in oil (East Texas solventtreated neutral) Soluble necked flask equipped with a mechanical stirrer. After the temperature reaches 250F. the source of heat is removed and 222 gms., 1 mole, of'phosphorus'pentasulfide is added in small increments over a minute period, the temperature of the exothermic reaction being thereby maintained at about 275 F. After the addition .of thelastincrement of the phosphorus pentasulfide, thereaction is continued for 12 hours at 275, F.,'following which 176 gms, 1 mole, of p-cyclehexylphenol is added. After further reaction for 10 hours at 275 F., the mixture is blended with 1022 gms. of a low viscosity Mid-Continent oil. 2% parts by weight of the resulting oil concentrate, after filtration, is mixed with 97% parts by weight of a Mid-Continent SAE 20 motor oil. This blend has an oifensive onion-like odor suggestive of mercaptans.

Example 3 Example .4

A 1400 gram sample of Pinene 111, from the same shipment as the Pinene 111 employed in Examples 2 and 3, is refluxed for about 1 hour with 28 grams of sodium'methylate powder, following which the mixture is subjected to a distilla-v tion in which a fraction boiling at 156-157 .C. is'taken as the product. Employed in the procedureof Example 3, this product gives a blend which is nearly odorless.

Example 5 A 19.5 grams of metallic potassium is dissolved in c. c. of anhydrous methanol and the solution added to 1000 grams of the Pinene 111. The

.excess alcohol is distilled on and the residual liquid refluxed for about 1 hour and distilled. A :portion of the distillate boiling at 156-157" C. is employed in the procedure of Example 3. The odor of the final blend is much less offensive than that of the final blend in the case of either Example 2 or Example 3.

Example 6 A kilogram of the Pinene 111 is refluxed for 1 hour with 30 grams sodium methylate (powder). The mixture is then distilled to separate materials boiling below C., and the residue cooled and filtered. A small volume of heavy liquid in the filtrate is separated by decantation and the remaining liquid refiltered until clear. A portion of the final filtrate, employed in the procedure of Example 3, gives a lblBI'ld having an odor equivalent to that of the blend of Example 5.

Example 7 A 1000 gram sample of the same Pinene 111 is refluxed for 24 hours over 20 grams barium oxide and then distilled. That portion of the distillate boiling at 156-157 C., employed according to the procedure of Example 2, gives a blend which is relatively odorless.

Example 8 A 3000 gram sample of the same Pinene 111 is refluxed for 5 hours over metallic sodium and then distilled to separate a fraction boiling at odorless as compared 1 tion for 8 hours to destroy peroxides.

1565157 C. When a portion of this fraction is employed according to Example 3, the ifinal blend is nearly odorless. A sample of ordinary turpen tine, treated in a similar manner, gives'a blend, which .while more odoriferous than the blend prepared; with the sodiumrtreated Pinene 111, is much superior in the respect of odor to a blend containing the turpentine phosphorus-sulfide reaction product prepared with untreated turpentine.

.. Example 9 A second portion of the fraction obtained in the distillation of Example 8 is employed according to Example 2. The final blend is relatively to the final blendof Ex- Example 10 Pinene 111, 1400 grams, was refluxed with 70 grams of a aqueous sodium hydroxide solu- The organic layer was separated and distilled through a fractionating column, the overhead collected boiling at 156157 C. The distillate was reacted and blended as in Example 3, giving a product with an odor equivalent tothe blend of that example.

I Example 11 Pinene 111, 750 grams, was refluxed with 15 grams sodium hydroxide (pellets) for 6 hours with stirring, and was then distilled. The distillate boiling at 156-157 C., was reacted and blended as in Example 3. The blend had an odor equivalent to that of the blends of Examples 2 and'3.

1 In" the appended claims, it is to be understood thatthe term turpentine embraces not only commercial wood tunpentine but also fractions such as the fractionatedturpentine marketed under the name Pinene 111 referred to in the forepart hereof and which consists predominately of alpha-rpinene.

I claim: 7 7 1,. As a new composition of matter, a product prepared-by the reaction, at a temperature approximating 200-300 of phosphorus sulfide With a fractionated turpentine initially consisting. essentially of about 92% of alpha-pinene,

from about 4 to about 5% of camphene, from about 3 to about 4% of dipentene together with compounds containing oxygen and from which only the compoundscontaining oxygen have been .removed, said product being capable ofinhibiting the deterioration of lubricating oils and retardingthe corrosion of metal-surfacescontacted. by

suchoils. I

2 A composition as in claim 1' in which said phosphorous sulfide is phosphorous pentasulfide. j I .3. A compounded lubricating oil having as .its

maior, component a mineral lubricating oil and as aminor component present in .a proportion approximating .0l%-1.0% an addend to repress its deterioration, said addend being further capable of retarding the corrosion of metal'surfaces to be contacted with the oil, said addend com- 4; A; compounded lubricating oil as in claim 3 in which said phosphorous sulfide is ;phos phorous pentasulfidei, l

5, As a new composition of matter, a derivative of a product prepared by the reaction, 'ata temperature approximating 200-30D F. of phosphorus sulfide with a fractionated turpentine initially consisting essentially of about 92% of alpha-pinene, from about 4 to about 5% of camphene, from about? to about 4% of dipentene together with compounds containing oxygen and from which only thecompounds containing oxygen have been removed, said derivative being capable of inhibiting the deterioration of lubricating oils and retarding the corrosion of metal surfaces contacted by such oils.

6. A compounded lubricating'oil 'having'as its major component a mineral lubricating oil and as a minor component'present in a proportion approximating .01%-1.0% an addend to, repress its deterioration, said addend being further capable of retarding the corrosion of metal surfaces to be contacted with the oil, said addend comprising a derivative of a product prepared by the reaction, at a temperature approximating 200300 F. of phosphorus sulfide with a fractionated turpentine initially consisting essentially of about 92% of alpha-pinene, from about 4 to about 5% of camphene, from about 3 to about 4% of dipentene together with compounds" containing oxygen and from which only the compounds containing oxygen have been removed.

7. As a new composition of matter the reaction product of an alkylated phenol and a condensation product produced by condensing ata tern perature approximating 200 300 F. phosphorus sulfide with a fractionated turpentine initially consisting essentially of about 92% of alphapinene, from about 4 to about 5% of camphene, from about 3 to about 4% of d ipentene'togethr with compounds containing oxygen and from which only the compounds containing oxygen have been removed, said reaction product being capable of inhibiting the deterioration of lubricating oils and retarding the corrosion of'metal surfaces contacted by such oils.

8. A compounded lubricating oil having as its major'component a mineral lubricating oil and as a minor component present in a proportion approximating 0.1%-l.0% an addend to repress its deterioration, said addend being further ca- ,pable of retarding the corrosion of metal surfaces to be contactedwith the 'oil, said addend comprising a reaction product of an, alkylated phenol with acondensation product produced by condensing, at a temperature approximating tionated turpentine initially consisting essentially of about 92% of alpha-pinene, from about pha-pinene, from about 4 to about 5% oicarpphene, from about 3 to about 4%. of dipentene together with compounds containing oxygen and from which only the compounds containing oxygen have been-removed, saidreaction product being capable of inhibiting the deteriorationof lubricating oils and retarding the corrosion of metal surfaces contacted by such oils.

10. A composition as lnclaim 9 in which said phosphorous sulfide is phosphorous pentasulfide.

11. A compounded lubricating oil having as its major component a mineral lubricating oil and as a minor component present in a proportion approximating .01 %-1.0% an addenci to repress its deterioration, said addend being further capable of retarding the corrosion of metal surfaces to be contacted with the-oil, said addend comprising a reaction product of a p-cyclohexyl phenol with a condensation product produced by condensing, at a temperature "approximating 200-300 F., phosphorus sulfide with a fractionated turpentine initially consisting essentially of about 92% of alpha-pinene, from about 4 to about 5% of camphene, from about 3 to about 4% of dipentene together with compounds containing oxygen and from which only the compounds containing oxygen have" been removed. 12. A compounded lubricating oil as in claim 11 in which said phosphorous sulfide is phosphorous pentasulflde.

FRANKLIN, WATKINS.

REFERENCES CITED The following references areot record in the flleot this patent: UNITED STATES PAiIfENTS OTHER REFERENCES (Organic Chemistry." Fleser and Fieser, 1944, Heath & 00., p. 49. 7 4 I 

1. AS A NEW COMPOSITION OF MATTER, A PRODUCT PREPARED BY THE REACTION, AT A TEMPERATURE APPROXIMATING 200*-300* F., OF PHOSPHORUS SULFIDE WITH A FRACTIONATED TURPENTINE INITIALLY CONSISTING ESSENTIALLY OF ABOUT 92% OF ALPHA-PINENE, FROM ABOUT 4 TO ABOUT 5% OF CAMPHENE, FROM ABOUT 3 TO ABOUT 4% OF DIPENTENE TOGETHER WITH COMPOUNDS CONTAINING OXYGEN AND FROM WHICH ONLY THE COMPOUNDS CONTAINING OXYGEN HAVE BEEN REMOVED, SAID PRODUCT BEING CAPABLE OF INHIBITING THE DETERIORATION OF LUBRICATING OILS AND RETARDING THE CORROSION OF METAL SURFACES CONTACTED BY SUCH OILS.
 3. A COMPOUNDED LUBRICATING OIL HAVING AS ITS MAJOR COMPONENT A MINERAL LUBRICATING OIL AND AS A MINOR COMPONENT PRESENT IN A POROPORTION APPROXIMATING .01%-1.0% AN ADDEND TO REPRESS ITS DETERIORATION, SAID ADDEND BEING FURTHER CAPABLE OF RETARDING THE CORROSION OF METAL SURFACES TO BE CONTACTED WITH THE OIL, SAID ADDEND COMPRISING A PRODUCT PREPARED BY THE REACTION AT A TEMPERATURE APPROXIMATING 200-300* F. OF PHOSPHORUS SULFIDE WITH A FRACTIONATED TURPENTINE INITIALLY CONSISTING ESSENTIALLY OF ABOUT 92% OF ALPHA-PINENE, FROM ABOUT 4 TO ABOUT 5% OF CAMPHENE, FROM ABOUT 3 TO ABOUT 4% OF DIPENTENE TOGETHER WITH COMPOUNDS CONTAINING OXYGEN AND FROM WHICH ONLY THE COMPOUNDS CONTAINING OXYGEN HAVE BEEN REMOVED. 